Assembling a Hybrid Pd Catalyst from a Chiral Anionic Co III Complex and Ligand for Asymmetric C(sp 3 )-H Functionalization.

An unusual hybrid palladium catalyst containing an anionic chiral Co-III complex and a chiral phosphoramidite ligand shows a high capacity for catalyzing asymmetric thioamide-directed C(sp(3))-H arylation and delivers excellent yield and enantioselectivity (up to 99% yield, 99% ee). Significant synergy between the chiral ligand and the anion in terms of stereochemical control was observed. Mechanistic investigations have revealed both the nature of the C-H activation and the origin of the enantioselectivity.